CN109704899A - The method that synthesis gas prepares alkene - Google Patents
The method that synthesis gas prepares alkene Download PDFInfo
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- CN109704899A CN109704899A CN201711010837.4A CN201711010837A CN109704899A CN 109704899 A CN109704899 A CN 109704899A CN 201711010837 A CN201711010837 A CN 201711010837A CN 109704899 A CN109704899 A CN 109704899A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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Abstract
The present invention relates to a kind of methods that synthesis gas prepares alkene, and it is long mainly to solve existing coal chemical technology production alkene route, and it is more to be related to technology type, invest larger, and manpower and material resources consumption is big, prepares the problem at high cost of alkene.The present invention is by using following steps: the reacted area of synthesis gas stream reacts to obtain product stream；Product stream is main carbonated logistics Ⅺ and decarburization logistics through the separation of decarburization area；Decarburization logistics is separated into mainly through dehydrogenation zone containing carbon monoxide, the circulation logistics of hydrogen and mixing hydrocarbon stream；The technical solution for being at least partly recycled back to reaction zone of above-mentioned circulation logistics preferably solves the above problem, can be used in low-carbon alkene production, has the advantages that short process flow, small investment, production cost are low.
Description
Technical field
The present invention relates to a kind of method that synthesis gas prepares alkene, especially a kind of one-step method from syngas prepares the side of alkene
Method.
Technical background
Alkene, especially ethylene, propylene and butylene are important basic chemical industry raw material, and in recent years, demand is continuous
Increase.Generally, alkene mostlys come from petroleum refining process.As the increasingly plaque of petroleum resources is weary, produced by petroleum resources
Ethylene, propylene cost be continuously increased, development by the non-oil resources such as coal or natural gas production alkene technology increasingly cause
Attention both domestic and external.
Current mature coal-to-olefin technology path, including coal gasification, purified synthesis gas, methanol-fueled CLC and methanol-to-olefins
Four core technologies.First synthesis gas is made in coal gasification by coal-to-olefin；Then synthesis gas is converted；Then by the conjunction after conversion
It is purified at gas；Crude carbinol and rectifying, the methanol of final output qualification finally is made in decontaminating syngas.It asks in the main face of coal-to-olefin
Topic mainly has: technology path is long, and number of devices is more, and plant investment is big, raw material and energy consumption is high, and water consume is high.
102666441 A of CN discloses the load-type iron-based catalyst used from synthesis gas production light alkene, passes through
Such as the method that Fischer-Tropsch (Fischer-Tropsch) technique produces light alkene from the raw material flow for including carbon monoxide and hydrogen,
Reaction temperature carries out at a temperature of being higher than 270 DEG C and only 500 DEG C, and carbon monoxide-olefin polymeric iron content particle has preferred lower than 20m
Ground is lower than the average particle size of 10nm.
102971277 A of CN is disclosed by synthesis gas production light olefin using ferrum-based catalyst, at 250~350 DEG C
The step of contacting synthesis gas and ferrum-based catalyst in temperature range and the pressure limit of 10~40 bars (bar), prepares light olefin
Such as C2~4The method of alkene.Range of the molar ratio of the H2:CO of synthesis gas 1.5~2.5.
103664447 A of CN discloses a kind of composition of the method catalyst of synthesis gas alkene, with molar ratio for 0.8
~2.2 CO and H2Gaseous mixture is raw material, at 250~350 DEG C of reaction temperature, 0.5~2.5MPa of reaction pressure, volume space velocity
1000~4000 hours-1Under conditions of, with catalyst haptoreaction generate alkene, wherein catalyst include based on parts by weight with
Lower component: 1~20 part of a kind of shell in ZSM-5 or β zeolite and 80~99 parts of kernel.
In terms of the prior art, prepare that alkene industrialization technology route is long, and designing technique type is more at present, investment compared with
Greatly, manpower and material resources consumption is big, and energy consumption is larger, it is also necessary to consume a large amount of water, the cost for preparing low-carbon alkene is accordingly higher.
In terms of the patent announced at present, the composition of catalyst production preparation process and catalyst is focused on mostly,
There are no the reaction for focusing on olefin product and separating technologies, and the invention proposes a kind of methods that synthesis gas prepares alkene, have
Targetedly solves the problems, such as this.
Summary of the invention
The technical problem to be solved by the present invention is to existing coal chemical technology production alkene route it is long, designing technique kind
Class is more, and investment is larger, and manpower and material resources consumption is big, prepares the at high cost of alkene, and synthesis gas preparation olefin reaction products separate
The high problem of energy consumption into hydrocarbon mixture logistics process complexity and separation process.A kind of method that synthesis gas prepares alkene is proposed,
Process flow is short, small investment, production cost are low, synthesis gas prepares olefine reaction production for having in the production of alkene for this method
The isolated hydrocarbon mixture logistics process of object is simple and separation process in the advantages of low energy consumption.
To solve the above problems, The technical solution adopted by the invention is as follows: a kind of method that synthesis gas prepares alkene, including
Following steps: a) the reacted area of synthesis gas stream reacts to obtain product stream；B) product stream mainly contains through the separation of decarburization area
The logistics Ⅺ and decarburization logistics of carbon dioxide；C) decarburization logistics is separated into the mainly circulation containing carbon monoxide, hydrogen through dehydrogenation zone
Logistics and mixing hydrocarbon stream；D) above-mentioned circulation logistics is at least partly recycled back to reaction zone.
In above-mentioned technical proposal, product stream includes carbon dioxide, carbon monoxide, hydrogen and hydrocarbon mixture.
In above-mentioned technical proposal, it is preferred that include in product stream, by weight percentage, 10%~40% titanium dioxide
Carbon, 1%~5% hydrogen, 30%~70% carbon monoxide, 10%~40% hydrocarbon mixture.
In above-mentioned technical proposal, it is preferred that by weight percentage, in product stream include 15%~35% titanium dioxide
Carbon.
In above-mentioned technical proposal, it is preferred that contain at least 60% C2~C4 hydrocarbon by weight percentage, in hydrocarbon mixture
Class.
In above-mentioned technical proposal, it is furthermore preferred that containing at least 70% C2~C4 hydrocarbon by weight percentage, in hydrocarbon mixture
Class.
In above-mentioned technical proposal, most preferably, contain at least 75% C2~C4 hydrocarbon by weight percentage, in hydrocarbon mixture
Class.
In technical solution of the present invention, at least the 60% of the circulation logistics is recycled back to reaction zone, preferably recycles logistics
At least 80% be recycled back to reaction zone, the preferred logistics that recycles all is recycled back to reaction zone.
In technical solution of the present invention, the decarburization area isolates carbon dioxide by absorbing the method for parsing.
In technical solution of the present invention, there is the generation of bicarbonate ion in the decarburization area.
In technical solution of the present invention, deep cooling separating method, PSA separation method and UF membrane side are used in the dehydrogenation zone
One of method or at least one isolate carbon monoxide or/and hydrogen.
In technical solution of the present invention, using one of PSA method and membrane separating method or combination in the dehydrogenation zone
Isolate carbon monoxide or/and hydrogen.
In technical solution of the present invention, the mixing hydrocarbon stream is subsequently through sequence separation method, front-end deethanization separation side
One of method, predepropanization separation method method carrys out isolated olefin product.
In technical solution of the present invention, the mixing hydrocarbon stream absorbs the separation combined subsequently through front-end deethanization and oil
Method carrys out isolated olefin product.
In technical solution of the present invention, the mixing hydrocarbon stream enters separative unit I, isolated C1~C2 logistics and C3
And the above logistics.
In technical solution of the present invention, the C3 and the above logistics enter the isolated C4 of separative unit II and the above logistics
With C3 logistics.
In technical solution of the present invention, C1~C2 logistics enters separative unit III, isolated C2 logistics and main
C1 logistics containing methane.
In technical solution of the present invention, at least partly C4 and the above object that the C1 logistics and separation of olefins unit II obtain
Stream enters separative unit IV, isolated methane stream and absorbing liquid logistics, and absorbing liquid logistics is returned to separative unit I.
In technical solution of the present invention, the carbon dioxide and methane that the decarburization area obtains are synthesized by reforming reaction
Gas.
In technical solution of the present invention, the reforming reaction obtains synthesis gas and is recycled back to reaction zone.
In technical solution of the present invention, the methane of the reforming reaction is isolated at least partially from separative unit IV
Methane.
In technical solution of the present invention, the reaction zone used catalyst system at least contains SAPO molecular sieve, AlPO4Point
One of son sieve is at least one.
In technical solution of the present invention, it is preferred that the reaction zone used catalyst system at least contains SAPO molecular sieve
And AlPO4Molecular sieve.
In technical solution of the present invention, it is preferred that molecular sieve is SAPO molecule in the reaction zone used catalyst system
Sieve and AlPO4Molecular sieve；It is furthermore preferred that SAPO molecular sieve and AlPO4The weight ratio of molecular sieve is (1:4)~(4:1).
In technical solution of the present invention, the synthesis gas stream mainly includes carbon monoxide and hydrogen.
In technical solution of the present invention, the synthesis gas stream is in terms of molal quantity, and hydrogen and carbon monoxide ratio are less than etc.
In 5.
In technical solution of the present invention, the synthesis gas stream is in terms of molal quantity, it is preferred that hydrogen and carbon monoxide ratio
Less than or equal to 3.
In technical solution of the present invention, the decarburization logistics mainly contain carbon monoxide, hydrogen, methane, ethylene, ethane,
Propylene, propane, C4+ hydro carbons.
In technical solution of the present invention, the mixing hydrocarbon stream mainly contains methane, ethylene, ethane, propylene, propane, C4+
Hydro carbons.
In technical solution of the present invention, decarburization area carbon-dioxide absorbent uses potassium carbonate and its homologous series sodium carbonate conduct
When absorbent, carbon dioxide is first hydrolyzed, and generates hydrogen ion and bicarbonate ion, and hydrogen ion is reacted with carbanion generates carbon
Sour hydrogen radical ion, i.e. carbon dioxide, water and carbonate reaction generate bicarbonate, to achieve the effect that absorbing carbon dioxide.
In another technical solution of the invention, decarburization area carbon-dioxide absorbent uses methyl diethanolamine and its homology
When column ethanol amine, diethanol amine, diisopropanolamine (DIPA) are as absorbent, carbon dioxide is first hydrolyzed, and generates hydrogen ion and bicarbonate radical
Ion, hydrogen ion and alcamines substance reaction generate the hydramine of protonation, i.e., carbon dioxide, water are reacted with hydramine generates bicarbonate
The hydramine of radical ion and protonation, to achieve the effect that absorbing carbon dioxide.
Inventor passes through the screening to decarburization area carbon-dioxide absorbent, it is believed that uses methyl diethanolamine and its homologous series
When ethanol amine, diethanol amine, diisopropanolamine (DIPA) are as absorbent, the energy is more saved.
In technical solution of the present invention, the scheme that the mixing hydrocarbon stream isolates olefin product has very much, can use
Sequence separation method, front-end deethanization separation are put the methods of method, predepropanization separation method and are separated, and inventor passes through to anti-
The research for answering product to be distributed, and the analogue simulation of a variety of separation methods is carried out, front-end deethanization and oil are used in the technical scheme
Absorb the separation scheme combined, it is thus only necessary to which propylene refrigeration compressor provides cooling capacity, has small investment, what low energy consumption is excellent
Gesture.
Sequence separation method refers in sequence from gently to the method that separation mixes hydrocarbon stream again, i.e., send mixing hydrocarbon stream
Enter domethanizing column first isolated methane and C2 and the above component, C2 and above group are distributed into dethanizer and obtain C2 component and C3
And the above component, C2 component are further separated out ethylene product, C3 and above group be distributed into depropanization alkane tower obtain C3 component and
C4 and the above component, C3 component are further separated out propylene product.
Front-end deethanization separation method refer to will mixing hydrocarbon stream be sent into dethanizer obtain C2 and following components and C3 and with
Upper component, C2 and following components are sent into domethanizing column, and first isolated methane and C2 component, C2 component are further separated out ethylene
Product, C3 and above group are distributed into depropanization alkane tower and obtain C3 component and C4 and the above component, and C3 component is further separated out third
Alkene product.
Predepropanization separation method refer to will mixing hydrocarbon stream be sent into depropanizing tower obtain C3 and following components and C4 and with
Upper component, C3 and following components are sent into dethanizer and obtain C2 and following components and C3 component, and C3 component is further separated out third
Alkene product, C2 and following components are sent into domethanizing column, and first isolated methane and C2 component, C2 component are further separated out ethylene
Product.
Above-mentioned three kinds of separation methods isolate methane and require ethylene cryogen needed for ethylene compressor provides separation, still
Methane content is seldom in product, absorbs the separation method combined more than front-end deethanization and oil using above-mentioned three kinds of formula investings
Height, economy are poor.
It can be seen that the technical solution adopted by the present invention from embodiment and comparative example, more existing coal chemical technology is in diene
Hydrocarbon yield, material consumption, energy consumption, waste water yield, investment carry out the preferred side that aspect has biggish advantage, especially the technical program
Case, advantage are more obvious.
Technical solution of the present invention passes through preferred decarburization area and dehydrogenation by the separating technology of preferably synthetic gas alkene
The series connection in area is gradually separated according to reasonable sequence, and not only unreacted raw material is fully used, and in low energy
In the case where consumption, Low investment, more diene products are obtained, good technical effect is achieved；Using technical side of the invention
Case can obtain good technical effect in composite catalyst of the routine containing SAPO molecular sieve, when using compound point preferred
When sub- sieve catalyst, the yield 2.2% of diene can further improve, the design flow of large-scale coal chemical industry is all million tons or more, i.e.,
Economic benefit can also be obviously increased by making the promotion of diene yield 0.1%；Energy consumption can be further decreased when preferred absorbent；When adopting
When the hydrocarbon mixture separation scheme combined with front-end deethanization and oil absorption, energy consumption can be also further decreased, more preferably skill can be obtained
Art effect.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the invention.
Fig. 2 is the flow diagram of mixing hydrocarbon separation method of the present invention.
In Fig. 1, Fig. 2,1 is synthesis gas stream, and 2 be product stream, and 3 be logistics Ⅺ, and 4 be decarburization logistics, and 5 be recycle
Stream, 6 be mixing hydrocarbon stream, and 7 be C1~C2 logistics, and 8 be C3 and the above logistics, and 9 be C2 logistics, and 10 be C1 logistics, and 11 be methane
Logistics, 12 be C3 logistics, and 13 be C4 and the above logistics, and 14 be part C4 and the above logistics, and 15 be absorbing liquid logistics, and 20 be reaction
Area, 21 be decarburization area, and 22 be dehydrogenation zone, and 23 be separative unit I, and 24 be separative unit III, and 25 be separative unit IV, and 26 be separation
Unit II.
In Fig. 1, synthesis gas stream (1) in the reaction region (20) reaction production containing carbon dioxide, carbon monoxide, hydrogen,
Methane, ethylene, ethane, propylene, propane, C4 +The product stream (2) of hydro carbons；Product stream (2) is separated into decarburization area (21)
Mainly contain the logistics Ⅺ (3) of carbon dioxide and mainly contain carbon monoxide, hydrogen, methane, ethylene, ethane, propylene, propane,
C4 +The decarburization logistics (4) of hydro carbons；Decarburization logistics (4) is separated into dehydrogenation zone (22) and to mainly contain carbon monoxide, hydrogen follows
Ring logistics (5) and mainly contain methane, ethylene, ethane, propylene, propane, C4 +The mixing hydrocarbon stream (6) of hydro carbons；It recycles logistics (5)
It is returned to reaction zone (20)；Mixing hydrocarbon stream (6) is further separated into olefin product in later separation area.
Separative unit I is sent into the separation method that Fig. 2 is combined using front-end deethanization and oil absorption, mixing hydrocarbon stream (6)
(23), separative unit III (24) are sent into isolated C1~C2 logistics (7) and C3 and the above logistics (8), C1~C2 logistics (7),
Separative unit IV (25) are sent into isolated C1 logistics (10) and C2 logistics (9), C1 logistics (10), isolated methane stream
(11) and absorbing liquid logistics (15), absorbing liquid logistics (15) are returned to separative unit I (23), and C3 and the above logistics (8), which are sent into, to divide
From unit II (26), isolated C3 logistics (12) and C4 and the above logistics (13), part C4 and the above logistics (14) are sent into and are divided
It is used as absorbing liquid from unit IV (25), C2 logistics (9) and C3 logistics (12) can further isolated olefin products.
Specific embodiment
Using feed coal needed for 1,800,000 tons/year of MTO technologies as benchmark, i.e., (technology path includes for existing coal chemical technology
Coal gasification, purified synthesis gas, methanol-fueled CLC and methanol-to-olefins) and technical solution of the present invention consumption feed coal it is identical
On the basis of, olefin product is prepared by existing coal chemical technology, is produced with alkene is prepared by technical solution of the present invention
Product compare the obtained olefin yield of two kinds of different technologies, material consumption, energy consumption, waste water yield, investment.
[embodiment 1]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.40% hydrogen, 46.40% carbon monoxide, 15.70% hydrocarbon mixture are sent into decarburization area, decarburization area
Using methyl diethanolamine as absorbent, dehydrogenation zone uses PSA separation method, and circulation logistics is all recycled back to reaction zone.This
The more existing coal chemical technology of diene (ethylene and propylene) increases by 5.50 ‰ in technical solution product stream, the more existing coal chemical industry of material consumption
Technology reduces 2.90%, and the more existing coal chemical technology of energy consumption reduces 21.26%, and the more existing coal chemical technology of waste water yield is reduced
100.4 ten thousand tons/year, the more existing coal chemical technology reduction 6.25% of investment.
[embodiment 2]
Molecular sieve is 80%SAPO molecular sieve and 20% AlPO in the catalyst system that reaction zone uses4Molecular sieve；Instead
The product stream for answering area to obtain includes: 25.00% carbon dioxide, 3.39% hydrogen, 46.39% carbon monoxide, 15.72% mixing
Hydro carbons is sent into decarburization area, and using methyl diethanolamine as absorbent, dehydrogenation zone uses PSA separation method, recycle in decarburization area
Stream is all recycled back to reaction zone.The more existing coal chemical technology of diene (ethylene and propylene) increases in the technical program product stream
9.63 ‰, the more existing coal chemical technology of material consumption reduces 2.92%, and the more existing coal chemical technology of energy consumption reduces 21.27%, and waste water produces
It measures more existing coal chemical technology and reduces by 100.4 ten thousand tons/year, the more existing coal chemical technology reduction 6.25% of investment.
[embodiment 3]
Molecular sieve is 50%SAPO molecular sieve and 50% AlPO in the catalyst system that reaction zone uses4Molecular sieve；Instead
The product stream for answering area to obtain includes: 25.00% carbon dioxide, 3.38% hydrogen, 46.38% carbon monoxide, 15.74% mixing
Hydro carbons is sent into decarburization area, and using methyl diethanolamine as absorbent, dehydrogenation zone uses PSA separation method, recycle in decarburization area
Stream is all recycled back to reaction zone.The more existing coal chemical technology of diene (ethylene and propylene) increases in the technical program product stream
9.63 ‰, the more existing coal chemical technology of material consumption reduces 2.94%, and the more existing coal chemical technology of energy consumption reduces 21.28%, and waste water produces
It measures more existing coal chemical technology and reduces by 100.4 ten thousand tons/year, the more existing coal chemical technology reduction 6.25% of investment.
[embodiment 4]
Molecular sieve is 20%SAPO molecular sieve and 80% AlPO in the catalyst system that reaction zone uses4Molecular sieve；Instead
The product stream for answering area to obtain includes: 25.00% carbon dioxide, 3.37% hydrogen, 46.37% carbon monoxide, 15.76% mixing
Hydro carbons is sent into decarburization area, and using methyl diethanolamine as absorbent, dehydrogenation zone uses PSA separation method, recycle in decarburization area
Stream is all recycled back to reaction zone.The more existing coal chemical technology of diene (ethylene and propylene) increases in the technical program product stream
9.64 ‰, the more existing coal chemical technology of material consumption reduces 2.96%, and the more existing coal chemical technology of energy consumption reduces 21.29%, and waste water produces
It measures more existing coal chemical technology and reduces by 100.4 ten thousand tons/year, the more existing coal chemical technology reduction 6.25% of investment.
[embodiment 5]
Molecular sieve is AlPO in the catalyst system that reaction zone uses4Molecular sieve；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.36% hydrogen, 46.36% carbon monoxide, 15.78% hydrocarbon mixture are sent into decarburization area, decarburization area
Using methyl diethanolamine as absorbent, dehydrogenation zone uses PSA separation method, and circulation logistics is all recycled back to reaction zone.This
The more existing coal chemical technology of diene (ethylene and propylene) increases by 8.62 ‰ in technical solution product stream, the more existing coal chemical industry of material consumption
Technology reduces 2.98%, and the more existing coal chemical technology of energy consumption reduces 21.30%, and the more existing coal chemical technology of waste water yield is reduced
100.4 ten thousand tons/year, the more existing coal chemical technology reduction 6.25% of investment.
[embodiment 6]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.35% hydrogen, 46.35% carbon monoxide, 15.70% hydrocarbon mixture are sent into decarburization area, decarburization area
Using methyl diethanolamine as absorbent, dehydrogenation zone uses PSA separation method, and circulation logistics 80% is recycled back to reaction zone.This
The more existing coal chemical technology of technical solution diene (ethylene and propylene) increases by 5.00 ‰, and the more existing coal chemical technology of material consumption is reduced
2.60%, the more existing coal chemical technology of energy consumption reduces 18.50%, the more existing coal chemical technology of waste water yield reduce 100.2 ten thousand tons/
Year, the more existing coal chemical technology of investment reduce 6.25%.
[embodiment 7]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.0% carbon dioxide, 3.4% hydrogen, 46.4% carbon monoxide, 15.7% hydrocarbon mixture are sent into decarburization area, and decarburization area uses
For methyl diethanolamine as absorbent, dehydrogenation zone uses PSA separation method, and circulation logistics 60% is recycled back to reaction zone.This technology
The more existing coal chemical technology of scheme diene (ethylene and propylene) increases by 4.50 ‰, and the more existing coal chemical technology of material consumption is reduced
2.30%, the more existing coal chemical technology of energy consumption reduces 15.74%, the more existing coal chemical technology of waste water yield reduce 100.0 ten thousand tons/
Year, the more existing coal chemical technology of investment reduce 6.25%.
[embodiment 8]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.40% hydrogen, 46.40% carbon monoxide, 15.70% hydrocarbon mixture are sent into decarburization area, decarburization area
Using diethanol amine as absorbent, dehydrogenation zone uses PSA separation method, and circulation logistics is all recycled back to reaction zone.This technology
The more existing coal chemical technology of diene (ethylene and propylene) increases by 5.50 ‰ in scheme product stream, the more existing coal chemical technology of material consumption
2.90% is reduced, the more existing coal chemical technology of energy consumption reduces 21.259%, and the more existing coal chemical technology of waste water yield reduces 100.4
Ten thousand tons/year, the more existing coal chemical technology reduction 6.25% of investment.
[embodiment 9]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.40% hydrogen, 46.40% carbon monoxide, 15.70% hydrocarbon mixture are sent into decarburization area, decarburization area
Using ethanol amine as absorbent, dehydrogenation zone uses PSA separation method, and circulation logistics is all recycled back to reaction zone.This technology side
The more existing coal chemical technology of diene (ethylene and propylene) increases by 5.50 ‰ in case product stream, and the more existing coal chemical technology of material consumption subtracts
Few 2.90%, the more existing coal chemical technology of energy consumption reduces 21.26%, and the more existing coal chemical technology of waste water yield reduces 100.4 ten thousand
Ton/year, the more existing coal chemical technology of investment reduce 6.25%.
[embodiment 10]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.40% hydrogen, 46.40% carbon monoxide, 15.70% hydrocarbon mixture are sent into decarburization area, decarburization area
Using sodium carbonate as absorbent, dehydrogenation zone uses PSA separation method, and circulation logistics is all recycled back to reaction zone.This technology side
The more existing coal chemical technology of diene (ethylene and propylene) increases by 5.50 ‰ in case product stream, and the more existing coal chemical technology of material consumption subtracts
Few 2.90%, the more existing coal chemical technology of energy consumption reduces 20.22%, and the more existing coal chemical technology of waste water yield reduces 100.4 ten thousand
Ton/year, the more existing coal chemical technology of investment reduce 6.25%.
[embodiment 11]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.40% hydrogen, 46.40% carbon monoxide, 15.70% hydrocarbon mixture are sent into decarburization area, decarburization area
Using potassium carbonate as absorbent, dehydrogenation zone uses PSA separation method, and circulation logistics is all recycled back to reaction zone.This technology side
The more existing coal chemical technology of diene (ethylene and propylene) increases by 5.50 ‰ in case product stream, and the more existing coal chemical technology of material consumption subtracts
Few 2.90%, the more existing coal chemical technology of energy consumption reduces 20.21%, and the more existing coal chemical technology of waste water yield reduces 100.4 ten thousand
Ton/year, the more existing coal chemical technology of investment reduce 6.25%.
[embodiment 12]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.40% hydrogen, 46.40% carbon monoxide, 15.70% hydrocarbon mixture are sent into decarburization area, decarburization area
Using 80% potassium carbonate and 20% diethanol amine as absorbent, dehydrogenation zone uses PSA separation method, and circulation logistics all recycles
Return reaction zone.The more existing coal chemical technology of diene (ethylene and propylene) increases by 5.50 ‰ in the technical program product stream, material consumption
More existing coal chemical technology reduces 2.90%, and the more existing coal chemical technology of energy consumption reduces 19.20%, the more existing coalification of waste water yield
Work technology reduces by 100.4 ten thousand tons/year, the more existing coal chemical technology reduction 6.25% of investment.
[embodiment 13]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.40% hydrogen, 46.40% carbon monoxide, 15.70% hydrocarbon mixture are sent into decarburization area, decarburization area
Using 50% sodium carbonate and 50% methyl diethanolamine as absorbent, dehydrogenation zone uses PSA separation method, and circulation logistics is whole
It is recycled back to reaction zone.The more existing coal chemical technology of diene (ethylene and propylene) increases by 5.50 ‰ in the technical program product stream,
The more existing coal chemical technology of material consumption reduces 2.90%, and the more existing coal chemical technology of energy consumption reduces 19.53%, and waste water yield is more existing
Coal chemical technology reduces by 100.4 ten thousand tons/year, the more existing coal chemical technology reduction 6.25% of investment.
[embodiment 14]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.40% hydrogen, 46.40% carbon monoxide, 15.70% hydrocarbon mixture are sent into decarburization area, decarburization area
Using 20% potassium carbonate and 80% ethanol amine as absorbent, dehydrogenation zone uses PSA separation method, and circulation logistics is all recycled back to
Reaction zone.The more existing coal chemical technology of diene (ethylene and propylene) increases by 5.50 ‰ in the technical program product stream, material consumption compared with
Existing coal chemical technology reduces 2.90%, and the more existing coal chemical technology of energy consumption reduces 19.86%, the more existing coal chemical industry of waste water yield
Technology reduces by 100.4 ten thousand tons/year, the more existing coal chemical technology reduction 6.25% of investment.
[embodiment 15]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.0% carbon dioxide, 3.4% hydrogen, 46.4% carbon monoxide, 15.7% hydrocarbon mixture are sent into decarburization area, and decarburization area uses
Methyl diethanolamine uses deep cooling separating method as absorbent, dehydrogenation zone, and the technical program diene (ethylene and propylene) is more existing
There is coal chemical technology to increase by 5.50 ‰, the more existing coal chemical technology of material consumption reduces 2.90%, and the more existing coal chemical technology of energy consumption subtracts
Few 19.60%, the more existing coal chemical technology of waste water yield reduces by 100.4 ten thousand tons/year, the more existing coal chemical technology reduction of investment
6.15%.
[embodiment 16]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.0% carbon dioxide, 3.4% hydrogen, 46.4% carbon monoxide, 15.7% hydrocarbon mixture are sent into decarburization area, and decarburization area uses
Methyl diethanolamine uses membrane separating method as absorbent, dehydrogenation zone, and the technical program diene (ethylene and propylene) is more existing
Coal chemical technology increases by 5.50 ‰, and the more existing coal chemical technology of material consumption reduces 2.90%, and the more existing coal chemical technology of energy consumption is reduced
21.32%, the more existing coal chemical technology of waste water yield reduces by 100.4 ten thousand tons/year, the more existing coal chemical technology reduction of investment
6.05%.
[embodiment 17]
Molecular sieve is AlPO in the catalyst system that reaction zone uses4Molecular sieve, changes reaction zone conditions, and reaction zone obtains
Product stream include: 36.50% carbon dioxide, 1.70% hydrogen, 23.40% carbon monoxide, 38.40% hydrocarbon mixture are sent
Enter decarburization area, using methyl diethanolamine as absorbent, dehydrogenation zone uses PSA separation method in decarburization area, and circulation logistics is whole
It is recycled back to reaction zone.The more existing coal chemical technology of diene (ethylene and propylene) increases by 13.45 ‰ in the technical program product stream,
The more existing coal chemical technology of material consumption reduces 7.09%, and the more existing coal chemical technology of energy consumption reduces 50.08%, and waste water yield is more existing
Coal chemical technology reduces by 100.4 ten thousand tons/year, the more existing coal chemical technology reduction 6.25% of investment.
[embodiment 18]
Molecular sieve is SAPO and AlPO in the catalyst system that reaction zone uses4Mixed molecular sieve；The production that reaction zone obtains
Product logistics includes: 16.55% carbon dioxide, 4.25% hydrogen, 63.20% carbon monoxide, 16.00% hydrocarbon mixture, is sent into de-
Carbon area, using methyl diethanolamine as absorbent, dehydrogenation zone uses PSA separation method in decarburization area, and circulation logistics all recycles
Return reaction zone.The more existing coal chemical technology of diene (ethylene and propylene) increases by 7.50 ‰ in the technical program product stream, material consumption
More existing coal chemical technology reduces 2.98%, and the more existing coal chemical technology of energy consumption reduces 21.40%, the more existing coalification of waste water yield
Work technology reduces by 100.4 ten thousand tons/year, the more existing coal chemical technology reduction 6.25% of investment.
[embodiment 19]
Using mixing hydrocarbon stream obtained by the embodiment of the present invention 1 as charging, mixing hydrocarbon stream by weight percentage, contains
Following components: 2.2% methane, 2.0% ethane, 14.6% ethylene, 2.7% propane, 35.5% propylene, 43.0%C4 and above group
Point.Mixing hydrocarbon separation method is according to Fig. 2 separation scheme of the present invention combined using front-end deethanization and oil absorption, only
Separation needs can be met by needing propylene refrigeration compressor to provide cooling capacity, this separate section energy consumption is that 339kg mark oil/ton alkene produces
Product, investment about 9.7 hundred million.
[embodiment 20]
Using mixing hydrocarbon stream obtained by the embodiment of the present invention 1 as charging, mixing hydrocarbon stream by weight percentage, contains
Following components: 2.2% methane, 2.0% ethane, 14.6% ethylene, 2.7% propane, 35.5% propylene, 43.0%C4 and above group
Point.Mix hydrocarbon separation method according to it is of the present invention use sequence separation method, energy consumption be 369kg mark oil/ton olefin product,
Investment about 10.41 hundred million.
[embodiment 21]
Using mixing hydrocarbon stream obtained by the embodiment of the present invention 1 as charging, mixing hydrocarbon stream by weight percentage, contains
Following components: 2.2% methane, 2.0% ethane, 14.6% ethylene, 2.7% propane, 35.5% propylene, 43.0%C4 and above group
Point.Mix hydrocarbon separation method according to it is of the present invention use front-end deethanization method, energy consumption be 350kg mark oil/ton olefin product,
Investment about 9.99 hundred million.
[embodiment 22]
Using mixing hydrocarbon stream obtained by the embodiment of the present invention 1 as charging, mixing hydrocarbon stream by weight percentage, contains
Following components: 2.2% methane, 2.0% ethane, 14.6% ethylene, 2.7% propane, 35.5% propylene, 43.0%C4 and above group
Point.Mix hydrocarbon separation method according to it is of the present invention use predepropanization method, energy consumption be 358kg mark oil/ton olefin product,
Investment about 10.08 hundred million.
[comparative example 1]
60.39 ten thousand tons/year of existing coal chemical technology olefin yield, material consumption are that 6 tons of coals/ton olefin product, energy consumption are
1869kg marks oil/ton olefin product, 100.4 ten thousand tons/year of waste water yield, investment about 89.7 hundred million.
[comparative example 2]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.40% hydrogen, 46.40% carbon monoxide, 15.70% hydrocarbon mixture are first sent into dehydrogenation zone, dehydrogenation
Area uses PSA separation method, is re-fed into decarburization area, and decarburization area, as absorbent, it is whole to recycle logistics using methyl diethanolamine
It is recycled back to reaction zone.The more existing coal chemical technology of diene (ethylene and propylene) increases by 5.50 ‰ in the technical solution product stream,
The more existing coal chemical technology of material consumption reduces 2.90%, and the more existing coal chemical technology of energy consumption reduces 5.26%, and waste water yield is more existing
Coal chemical technology reduces by 100.4 ten thousand tons/year, the more existing coal chemical technology increase by 1.25% of investment.
[comparative example 3]
Molecular sieve is SAPO molecular sieve in the catalyst system that reaction zone uses；The product stream that reaction zone obtains includes:
25.00% carbon dioxide, 3.40% hydrogen, 46.40% carbon monoxide, 15.70% hydrocarbon mixture are first sent into dehydrogenation zone, dehydrogenation
Area uses deep cooling separating method, is re-fed into decarburization area, and decarburization area, as absorbent, it is whole to recycle logistics using methyl diethanolamine
It is recycled back to reaction zone.The more existing coal chemical technology of diene (ethylene and propylene) increases by 5.50 ‰ in the technical solution product stream,
The more existing coal chemical technology of material consumption reduces 2.90%, and since carbon dioxide exists, cryogenic separation cannot go on, and cannot get alkene
Hydrocarbon product, energy consumption cannot calculate.
Claims (18)
1. a kind of method that synthesis gas prepares alkene, includes the following steps:
A) the reacted area of synthesis gas stream reacts to obtain product stream；
B) product stream is main carbonated logistics Ⅺ and decarburization logistics through the separation of decarburization area；
C) decarburization logistics is separated into mainly through dehydrogenation zone containing carbon monoxide, the circulation logistics of hydrogen and mixing hydrocarbon stream；
D) above-mentioned circulation logistics is at least partly recycled back to reaction zone.
2. the method that synthesis gas according to claim 1 prepares alkene, it is characterised in that recycle logistics at least 60% follows
Loopback reaction zone.
3. the method that synthesis gas according to claim 2 prepares alkene, it is characterised in that recycle logistics at least 80% follows
Loopback reaction zone.
4. the method that synthesis gas according to claim 3 prepares alkene, it is characterised in that circulation logistics is all recycled back to instead
Answer area.
5. the method that synthesis gas according to claim 1 prepares alkene, it is characterised in that decarburization area is by absorbing parsing
Method isolates carbon dioxide.
6. the method that synthesis gas according to claim 5 prepares alkene, it is characterised in that there is bicarbonate ion in decarburization area
Generation.
7. the method that synthesis gas according to claim 1 prepares alkene, it is characterised in that use cryogenic separation in dehydrogenation zone
One of method, PSA separation method and membrane separating method or at least one isolate carbon monoxide or/and hydrogen.
8. the method that synthesis gas according to claim 7 prepares alkene, it is characterised in that in dehydrogenation zone using PSA method and
Carbon monoxide or/and hydrogen are isolated in one of membrane separating method or combination.
9. the method that synthesis gas according to claim 1 prepares alkene, it is characterised in that mixing hydrocarbon stream is subsequently through suitable
One of sequence separation method, front-end deethanization separation method, predepropanization separation method method carrys out isolated olefin product.
10. the method that synthesis gas according to claim 1 prepares alkene, it is characterised in that mixing hydrocarbon stream is subsequently through preceding
The separation method that deethanization and oil absorption combine carrys out isolated olefin product.
11. the method that synthesis gas according to claim 10 prepares alkene, it is characterised in that mixing hydrocarbon stream enters separation
Unit I, isolated C1~C2 logistics and C3 and the above logistics.
12. the method that synthesis gas according to claim 10 prepares alkene, it is characterised in that C3 and above logistics entrance point
C4 isolated from unit II and the above logistics and C3 logistics.
13. the method that synthesis gas according to claim 10 prepares alkene, it is characterised in that C1~C2 logistics enters separation
Unit III, isolated C2 logistics and the C1 logistics for mainly containing methane.
14. the method that synthesis gas according to claim 10 prepares alkene, it is characterised in that C1 logistics and separation of olefins list
At least partly C4 and the above logistics that member II obtains enter separative unit IV, isolated methane stream, isolated methane object
Stream and absorbing liquid logistics, absorbing liquid logistics are returned to separative unit I.
15. the method that synthesis gas according to claim 1 prepares alkene, it is characterised in that the carbon dioxide that decarburization area obtains
Synthesis gas is obtained by reforming reaction with methane.
16. the method that synthesis gas according to claim 1 prepares alkene, it is characterised in that reforming reaction obtains synthesis gas and follows
Loopback reaction zone.
17. the method that synthesis gas according to claim 1 prepares alkene, it is characterised in that the methane of reforming reaction at least portion
Divide the methane isolated from separative unit IV.
18. the method that synthesis gas according to claim 1 prepares alkene, it is characterised in that the reaction zone used catalyst
System at least contains SAPO molecular sieve, AlPO4One of molecular sieve or at least one.
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